EP0087462A1 - Process for manufacturing an integrated circuit structure. - Google Patents

Process for manufacturing an integrated circuit structure.

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Publication number
EP0087462A1
EP0087462A1 EP82902885A EP82902885A EP0087462A1 EP 0087462 A1 EP0087462 A1 EP 0087462A1 EP 82902885 A EP82902885 A EP 82902885A EP 82902885 A EP82902885 A EP 82902885A EP 0087462 A1 EP0087462 A1 EP 0087462A1
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EP
European Patent Office
Prior art keywords
substrate
oxide
mask
nitride
layer
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Granted
Application number
EP82902885A
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German (de)
French (fr)
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EP0087462B1 (en
EP0087462A4 (en
Inventor
Samuel Yue Chiao
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Ncr International Inc hyundai Electronics America
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NCR Corp
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Publication of EP0087462A1 publication Critical patent/EP0087462A1/en
Publication of EP0087462A4 publication Critical patent/EP0087462A4/en
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Publication of EP0087462B1 publication Critical patent/EP0087462B1/en
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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/26Bombardment with radiation
    • H01L21/263Bombardment with radiation with high-energy radiation
    • H01L21/265Bombardment with radiation with high-energy radiation producing ion implantation
    • H01L21/26506Bombardment with radiation with high-energy radiation producing ion implantation in group IV semiconductors
    • H01L21/26513Bombardment with radiation with high-energy radiation producing ion implantation in group IV semiconductors of electrically active species
    • H01L21/2652Through-implantation
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/033Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/225Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
    • H01L21/2251Diffusion into or out of group IV semiconductors
    • H01L21/2252Diffusion into or out of group IV semiconductors using predeposition of impurities into the semiconductor surface, e.g. from a gaseous phase
    • H01L21/2253Diffusion into or out of group IV semiconductors using predeposition of impurities into the semiconductor surface, e.g. from a gaseous phase by ion implantation
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/26Bombardment with radiation
    • H01L21/263Bombardment with radiation with high-energy radiation
    • H01L21/265Bombardment with radiation with high-energy radiation producing ion implantation
    • H01L21/266Bombardment with radiation with high-energy radiation producing ion implantation using masks
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/76Making of isolation regions between components
    • H01L21/762Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers
    • H01L21/76202Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using a local oxidation of silicon, e.g. LOCOS, SWAMI, SILO
    • H01L21/76213Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using a local oxidation of silicon, e.g. LOCOS, SWAMI, SILO introducing electrical inactive or active impurities in the local oxidation region, e.g. to alter LOCOS oxide growth characteristics or for additional isolation purpose
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S438/00Semiconductor device manufacturing: process
    • Y10S438/942Masking
    • Y10S438/944Shadow

Definitions

  • This invention relates to processes of the kind for forming an oxide region in a portion of a semiconductor substrate, including the steps of: forming a silicon oxide layer on a surface of said substrate and forming a silicon nitride layer on a portion of said oxide layer and having edges defining an active area of the substrate.
  • LOCOS process A process referred to as the LOCOS process is known from the publication "Local Oxidation of Silicon: New Technological Aspects" by J. A. Appels et al, Philips Research Reports 26, pages 157-165, June 1971.
  • relatively thick oxide patterns are partly or fully countersunk in the silicon substrate by utilizing the composite silicon oxidesilicon nitride layer as an oxidation mask. If the composite silicon oxide-silicon nitride layer is first used as an etchant mask before oxidation then a fully countersunk oxide pattern is obtained.
  • an undesired oxide extension known as the "bird's beak” grows underneath the silicon nitride mask.
  • a bump which may be of the order of 4,000-5,000 Angstroms in height is formed in the edge of the thick oxide layer adjoining the oxidenitride mask.
  • the bird's beak is formed in the recessed oxide during oxidation and results from lateral diffusion underneath the silicon dioxide (also known as pad oxide) which is formed between the silicon substrate and the silicon nitride.
  • the bird's head results from the higher specific volume of the silicon dioxide than silicon and the lateral oxidation which occurs at the sidewalls of the recess.
  • the silicon dioxide pad is used to prevent damage to the underlying silicon substrate by minimizing the stresses created on the substrate by the silicon nitride-silicon interface. Such stresses induce dislocations in the silicon substrate which result in undesirable leakage current channels and otherwise have a deleterious effect on the electrical characteristics of the interface.
  • U.S. Patent Specification No. 3,958,040 According to this known process, recesses are etched in the silicon substrate where fully recessed oxide is desired. Then an additional nitride mask is provided on the side walls of the recesses to protect the underlying silicon against oxidation, thereby reducing the bird's head formation. By providing the additional mask to adjoin the nitride layer of the first mask, it may be possible to reduce the extent of the bird's beak as well as the bird's head.
  • the known process has the disadvantage that control of the bird's head problem is limited since when etching the recesses in the silicon some silicon will tend to remain on the underside of the mask overhang. If it is attempted to severely over-etch the substrate to fully remove such remaining silicon then the overhanging mask may collapse. Another disadvantage is that the nitride mask over the sidewalls of the recesses has only a limited degree of effectiveness during the oxidation step.
  • a further disadvantage is that only limited control of the bird's beak problem is achieved by the known process because some lateral oxidation of the silicon oxide layer of the composite mask still occurs.
  • a process of the kind specified characterized by the steps of: forming a mask on said nitride layer having at least one edge projecting a predetermined distance beyond said nitride layer; forming a doped region in said substrate having an edge the location of which relative to an edge of said nitride layer is determined by the projecting edge of said mask; and thermally oxidizing said substrate thereby converting at least a portion of said doped layer to an oxide region.
  • a process according to the invention has the capability of significantly reducing both the bird's beak and the bird's head.
  • a further advantage is the capability of precise control of active region dimensions.
  • the step of thermally oxidizing the substrate is effected at a temperature of below about 800oC.
  • a preferable range for such thermal oxidation is 700-800oC.
  • Figs. 1-7 are cross-sectional representations of the sequential stages of fabricating a true coplanar semiconductor structure using the processes of the present invention.
  • Figs. 1, 2, 3A, 5A, 6A and 7 are cross sectional representations of forming a true coplanar structure using an alternative process of the present invention.
  • Figs. 1-5 and 8 are cross-sectional representations of the sequential stages of fabricating a standard coplanar semiconductor structure using a process of the present invention.
  • Figs. 1-5, 6B, and 9 are cross-sectional representations of the sequential stages of forming a true coplanar semiconductor structure having a bird's beak and/or bird's head using a modified process.
  • Fig. 10 is a cross-sectional representation of a true coplanar structure fabricated in accordance with the present invention showing a conventional integrated circuit formed thereon.
  • Table I is an outline of the process sequence for forming a standard coplanar structure having a reduced bird's beak and bird's head in accordance with the present embodiment.
  • Steps 1 to 8 and 13 refer to the standard coplanar structure and steps 1 to 13 refer to the t ⁇ ue coplanar structure. While the following description is primarily directed toward the fabrication of the standard and true coplanar integrated circuit structures, this description is exemplary of the fabrication of a class of integrated circuit structures which embody the principles of the present invention.
  • the thickness and other dimensions shown in the drawings herein are selected for clarity of illustration and not to be interpreted in a limiting sense there are a number of parameters whose dimensions are important.
  • the starting material is a slice of n-type or p-type monocrystalline semiconductor grade silicon.
  • the starting material can be of either (111) or (100) orientation and has a bulk resistivity typically of 8-12 ohmcentimeter.
  • the substrate 10 represents only a very small undivided part of the slice, perhaps 1 mil (about 25.4 microns) wide for each part.
  • the slice is oxidized (step 2) by exposing, typically, to pure, dry oxygen at a rate of 5 liters per minute in a furnace tube at an elevated temperature of perhaps 850-1000oC to produce an oxide layer 11 (Fig. 1) over the entire slice to a thickness of about 100-500 Angstroms.
  • the thermal oxidation may be accomplished at atmospheric pressure or at a high pressure of up to 7 atmospheres.
  • the oxide layer 11 (also referred to herein as pad oxide) may also be formed by wet oxidation by passing oxygen gas through water maintained at 97°C, at the same flow rate as before, prior to admitting the oxygen into the furnace tube.
  • the temperature of wet oxidation is also in the range of 850-1000°C.
  • a silicon nitride layer 12 is deposited (step 3) on the silicon slice, by low temperature chemical vapor deposition (LPCVD) using a mixture of ammonia and dichlorosilane at a temperature of about 700oC and a pressure of 400 millitorr. A typical ratio of ammonia to dichlorosilane is 3.5:1.
  • the thickness of nitride 12 formed in this manner is typically in the range of 700-1800 Angstroms. The lower limit here corresponds to the minimum thickness of the nitride needed to avoid defects in the nitride through which unwanted oxygen penetration may occur at a subsequent stage of fabrication of the present device.
  • the nitride 12 may strain the surface of the silicon substrate 10 to a degree that the substrate surface will develop dislocations and defects resulting in unwanted junction leakage.
  • the surface portion of the nitride layer may be oxidized (step 4) to form a thin surface layer 13 (Fig. 1) of silicon dioxide. This may be done by treating the nitride 12 with steam at 750-1000oC or by LPCVD at a temperature of 400-500oC for a time sufficient to form a silicon dioxide layer 13 of about 50-100 Angstroms thickness.
  • this step is not essential to the concept of the present invention per se, it is believed preferable to use this step to enhance adhesion of the nitride 12. to the next to be formed photoresist layer.
  • a layer of photoresist 14 of typical thickness in the range 6,000-10,000 Angstroms is applied over the entire surface of the resulting structure using a conventional process, then exposed to ultraviolet light through a mask which defines the desired pattern of the device active area.
  • the photoresist is then developed by using a suitable solvent exposing the areas where the nitride is to be etched away.
  • this thin oxide layer is removed by dipping the slice in a dilute hydrofluoric acid solution.
  • the nitride layer 12 is then etched (step 5) using the overlying photoresist 14 (Fig. 2) as a mask by a conventional etching technique such as plasma etch or a wet chemical etch.
  • the nitride etch discussed in the previous step is accomplished in a controlled manner such that the nitride 12 is undercut resulting in a critical overhang 14A of length X L p of the photoresist 14 past the edge of the nitride 12 as shown in Fig. 2.
  • the length of the overhang X L P is the distance between edge 16 of the photoresist overhang 14A and edge 17 of the nitride mask 12.
  • This photoresist overhang 14A is necessary to protect the regions of the substrate directly beneath the nitride-oxide dual mask from being doped in the next to follow ion implantation step of the present process as fully explained hereiribelow.
  • the length X L P of the overhang chosen for reducing the bird's beak and bird's head is a function of such parameters as the ion implantation energy, dose and drive-in depth which will become meaningful subsequently.
  • the structure is subjected to a conventional ion implantation step (step 6) whereby, for example, arsenic ions of a high energy in the range 80-100 Kev and dose 8 x 10 15 ions per square centimeter are introduced into the unmasked regions of the substrate through the oxide layer 11.
  • a conventional ion implantation step step 6
  • arsenic ions of a high energy in the range 80-100 Kev and dose 8 x 10 15 ions per square centimeter are introduced into the unmasked regions of the substrate through the oxide layer 11.
  • Other suitable dopants include phosphorus.
  • the profile of the dopant following this implantation step is shown in Fig. 3 by numeral 15.
  • the areas of the substrate where the bird's beak and bird's head are generally formed namely, the areas of the substrate directly beneath the photoresist overhang 14A and between the boundary lines 16 and 17, are protected by the photoresist overhang 14A and thus are not doped.
  • the photoresist 14 is removed and the implanted arsenic ions are diffused (step 7) into the substrate to a predetermined junction depth X J as shown in Fig. 4, which is an enlarged illustration of a section of the structure shown in Fig. 3, using a conventional diffusion process.
  • the profile of the dopant following the diffusion step is shown in Fig. 4 by numeral 15A.
  • the junction depth X. is determined by the thickness t ox of the recessed isolation oxide. The thicker the isolation oxide needed, the greater the depth X j .
  • the thickness of the doped silicon consumed during oxidation (step 8) is about 50% of the silicon dioxide grown therefrom, or
  • X j 0.5t ox (1)
  • the ions are diffused preferably to a depth X j of about 0.5 microns.
  • the implanted structure is subjected to a temperature of 1000oC in a nitrogen atmosphere for about 120 minutes. During this diffusion step/ the arsenic ions diffuse not only in the vertically downward direction but also laterally.
  • the sideways diffusion distance X d which is measured from the boun dary line corresponding to the edge I7 orf the overhang 14A (Fig. 4) is a function of the dopant dose and is generally less than the vertical diffusion distance X j .
  • X d is about 70% of the vertical diffusion.
  • X d 0.7X j (2)
  • the corresponding sideways diffusion distance X d would be about 0.35 microns.
  • the sideways diffusion distance X d would, of course, be less.
  • the sideways diffusion would be only about 50% of the vertical diffusion.
  • the latbearal a31.ffaa.sion distance would be 0.35 microns and -0.45 micr ons, respectively.
  • the lateral diffusion distance corresponding to the isolation oxide thickness of 10,000 Angstroms (1 micron) and 13,000 Angstroms (1.3 microns) are, respectively, 0.25 microns and 0.32 microns.
  • the length X L p of the overhang 14A is arranged preferably to be somewhat less than the lateral diffusion distance X,.
  • X L P is less than X d
  • the area of the substrate directly beneath the nitride is not doped during the implantation step (step 6), although the areas of the substrate beneath the nitride 12 and interior to the nitride boundary 17-17 may be doped during the diffusion step (step 7).
  • the doping in the regions just mentioned is light compared to that in the regions outside the boundary 17-17, providing rapid oxidation outside the boundary 17-17 and slower oxidation beneath the nitride 12 during the next-to-follow oxidation step (step 8) thereby substantially eliminating the bird's beak and bird's head.
  • the substrate area directly beneath the nitride 12 is not doped during either the implantation step (step 6) or the diffusion step (step. 7).
  • This provides rapid oxidation outside the nitride boundary 17-17 and slower oxidation beneath the nitride 12 and thereby eliminates the bird's beak and bird's head.
  • a nitride-edge which will be ragged and/or illdefined.
  • Such an improperly cut nitride mask will imprecisely define the active region causing design rule errors in subsequent device fabrication.
  • a low temperature steam oxidation is accomplished (step 8) to grow the thick field oxide regions 18 (Fig. 5) in the doped areas 15-15 (Fig. 4) of the substrate by consuming the silicon therein.
  • the temperature selected for this oxidation step is in the range 700-800°C and the time of oxidation is about 15-24 hours depending on the thickness of the field oxide regions 18 desired.
  • oxidation of the undoped regions of the substrate will be minimal thereby suppressing the bird's beak and bird's head.
  • the suppression of bird's beak and bird's head is achieved because silicon dioxide has different growth rates depending upon the silicon surface on which it is formed.
  • the growth rate of silicon dioxide from the highly doped silicon region 15- 15 is significantly greater than that of the intrinsic or undoped silicon corresponding to the nitride mask 12.
  • the growth rate is a function of the crystal orientation of the doped silicon surface, the rate for (111) surface being about 10-20% higher than that for a (100) surface and also the energy and dose of the ions used for doping (if accomplished by ion implantation) the silicon.
  • the oxide growth rate in the doped regions at the low temperature of 750oC is about 5-6 times higher than in the undoped regions of the same material.
  • the oxide growth rate increases as the impurity concentration increases.
  • the difference in oxidation rate between doped and undoped silicon also increases as the oxidation temperature becomes lower.
  • the temperature for the thermal oxidation in accordance with this invention lies between 700°C and 800°C when the ambient pressure is about one atmosphere since under these conditions it is possible to grow a 10,000-12,000 Angstrom thick field isolation oxide within a more manageable time of about 15-24 hours. It is appreciated that the oxidation rate becomes greater with increasing ambient pressure and the oxidation time can be made shorter or the oxidation temperature may be lowered below 700°C for a predetermined thickness.
  • the substrate areas where bird's beak and bird's head are formed are protected from doping during the ion implantation step and the diffusion step by means of the photoresist overhang 14A and then, by conveniently employing the different growth rates of silicon dioxide in doped/undoped silicon, the growth of bird's beak and bird's head is considerably decreased.
  • the thickness of the field oxide regions 18 (Fig. 5) grown as explained above is typically in the range of 10,000-12,000 Angstroms.
  • the oxide-nitride dual mask 11-12 is removed in the usual manner by first dipping the structure in dilute hydrofluoric acid to remove any oxide film that is formed over the nitride 12 during the previous oxidation step, then subjecting the nitride to an etchant such as hot phosphoric acid or a plasma which removes the nitride but not the silicon dioxide, followed by a re-dipping in dilute hydrofluoric acid to remove the pad oxide 11. Thereafter, the exposed silicon is cleaned.
  • the resulting structure is an improved standard coplanar structure, shown in Fig. 8, having a suppressed bird's beak and bird's head.
  • Example 1 Standard Coplanar Structure In a specific example of the process for forming a standard coplanar structure having about 10,000 Angstroms thick isolation oxide regions with a suppressed bird's beak and bird's head as exemplified by the process discussed above, after forming a 500 Angstrom thick pad oxide (11) and an i800 Angstrom thick nitride (12) composite mask (steps 2 and 3) on an n-type silicon substrate, the active region was patterned (step 5) using a photoresist 14 of thickness of about 8,000 Angstroms. Then, the nitride 12 was etched from the field regions, simultaneously creating the photoresist overhang 14A of length X L P in the range of about (0.1-
  • arsenic ions of energy 100 keV and dose about 8 x 10 15 ions per square centimeter were implanted in the field regions (step 6). Thereafter, the arsenic ions were diffused into the silicon sub strate to a depth of about 0.5 microns by subjecting the structure to a temperature of about 1000oC for about two hours in a nitrogen environment (step 7 ).
  • diffusion time and temperature chosen in this example the sideways diffusion X d of arsenic was about 0.35 microns.
  • the doped field regions were oxidized at a temperature of about 750oC for a period of about 20 hours, fully converting the doped silicon surface into a 10,000 Angstrom thick field oxide (step 8).
  • the pad oxide 11 and nitride 12 were then removed (step 13).
  • the thick field oxide formation (Fig. 5) surface is subjected to dilute hydrofluoric acid etch (step 9) for about 6-7 minutes to remove the field oxide and thereby form a mesa of silicon (10)- silicon dioxide (11)-silicon nitride (12) as shown in Fig. 6.
  • the oxide etch in this step not only removes substantially all the field oxide 18 forming the recesses 20 in the substrate, but also forms the nitride overhang 12A.
  • the nitride overhang 12A is tailored, by controlling the etch time in step 9, to have an overhang length X L n .
  • the length X L n of the overhang 12A is chosen such that the substrate regions beneath regions 11A of the pad oxide 11 where the bird's beak and bird's head are generally formed are protected from doping during the second field doping (steps 10 and 11) discussed below. This is analogous to the protec- tion of substrate region beneath the nitride 12 and interior to the nitride boundary 17-17 (Fig. 3) during the previously described fabrication process of Table I, step 5.
  • the length X L n like the photoresist overhang length X L P discussed in connection with step 5 above and for the reasons discussed therein, is arranged to be somewhat less than the lateral diffusion distance X d , of the dopant at the completion of the diffusion step 11 discussed, below.
  • the value of the nitride overhang length X L n which is necessary to suppress the bird's beak and bird's head is also ultimately determined by the thickness of the final field isolation oxide.
  • the exemplary parameters such as the vertical drive in depth X j (at the completion of step 10) of about 0.5 microns (which dimension is chosen to grow a 10,000 Angstrom thick final isolation oxide) and the lateral diffusion X d (at the completion of step 11) of about 0.35 microns when X L n is about (0.1-0.2) microns.
  • a dopant such as arsenic or phosphorus is ion implanted in the field regions (step 10).
  • Arsen ic ions of a relatively low energy in the range of 30-50 KeV and a dose preferably of the same value as in the first implantation (step 6, Table I) of 8 x 10 15 ions per square centimeter are used in this implantation step.
  • Lower energy arsenic ions are selected for the present field doping step than those used in step 6, since now the photoresist layer 14 (Figs. 2-4) is no longer present to protect the active region from high energy ion implantation.
  • the energy selected in the present step which is governed by the thickness of the nitride mask 12, is such that arsenic ions will not penetrate the nitride mask 12.
  • the structure is subjected to a high temperature diffusion (step 11) using the same conditions as explained in connection with step 7 above to diffuse the ions into the recesses 20 of the substrate.
  • a low temperature oxidation (step 12), which can use the same conditions as those discussed above in connection with the first field oxidation (step 8) is achieved to grow the final field oxide regions 21 shown in Fig. 7.
  • the low temperature oxidation of the present process step is continued for about 15-24 hours until the upper surface of the field isolation oxide regions matches the surface of the active region of the silicon substrate 10.
  • the oxide-nitride composite mask 11-12 is removed (step 13) in a conventional manner as fully explained above in connection with the standard coplanar structure.
  • the resulting structure as illustrated in Fig. 7 has a true coplanar surface with a plurality of recessed oxide isolation regions 21.
  • step 10 were then ion implanted (step 10) by means of arsenic ions of energy of about 40 keV and dose about 8 x 10 ions per square centimeter. Thereafter, the arsenic ions were diffused into the substrate (step 11) using the same conditions explained above in connection with this Example 2 to a depth of about 0.5 microns. This particular junction facilitated growing a 10,000 Angstrom thick final isolation oxide 21 (Fig. 7). Following the diffusion of arsenic, a second low temper- ature oxidation (step 12) using the same conditions as explained above in connection with the present Example was accomplished growing the field oxide regions 21 (Fig. 7) until the upper surface of these oxide regions matched the active region of the silicon substrate. The oxide (11)-nitride (12) -mask was then removed.
  • the sequence of steps in this method follows the sequence of the previous method of forming a true coplanar structure described above and illustrated in Table I through the step of ion implantation in the field regions (step 6, Table I).
  • the energy and dose of ions used in this implantation step are the same as before, namely, when arsenic dopant is utilized, of about 80-100 keV and 8 x 10 ions per square centimeter, respectively.
  • the arsenic diffusion (step 7') departs from the previous process in that after implantation, the arsenic ions are driven deep into the silicon material (Fig.
  • the lower limit corresponds to forming a recessed isolation oxide of thickness of about 10,000 Angstroms.
  • the upper limit corresponds to an oxide thickness of about 13,000 Angstroms.
  • a low temperature steam oxidation (step 8'), at a temperature in the range 700-800oC for about twenty-four hours is applied to partially convert the doped silicon to silicon dioxide, leave some arsenic dopant in the lower strata of substrate 10 where the dopant was introduced during the implantation and diffusion steps (steps 6 and 7', respectively).
  • this oxidation step (step 8') about half of the doped silicon is converted to silicon dioxide leaving behind in the substrate a doped layer of a thickness in the range of about (0.35- 0.5) microns.
  • the exact thickness of the doped silicon left after the oxidation step 8' is determined by the final isolation oxide thickness desired and the amount of silicon dioxide that is to be left behind after the next-to-follow etching step (step 9'). If during step 9, all of the grown oxide 18 (Fig. 5A) is to be removed, and if the desired final isolation oxide thickness is about 10,000 Angstroms, then a doped silicon of thickness of about 0.5 microns be left beneath the oxide regions 18 (Fig. 5A) after the oxidation step (step 8').
  • step 9' a doped silicon of thickness of about 0.4 microns is sufficient.
  • the thickness of the oxide 18 (Fig. 5A) grown is typically in the range of 10,000-13,000 Angstroms.
  • the grown oxide 18 is etched (step 9') in a conventional manner resulting in the recesses 20 in the substrate and a silicon (10)-oxide (11)-nitride (12) mesa (Fig. 6A). During this etching step, the sidewalls 19 (Fig.
  • Example 3 True Coplanar Structure
  • the steps of Example 2 above through the step of arsenic diffusion were carried out.
  • the arsenic ions were diffused at 1000oC for about 2.5 hours such that the junction depth, (Fig. 3A) at the completion of this step was about 0.8 microns (step 7', Table II).
  • the thick oxide regions 18 Fig.
  • the above described process may be modified to construct a planar structure where suppression of bird's beak and bird's head is not a concern.
  • This is achieved by following the process sequence shown in Table I through step 9, the step of etching the grown oxide and forming the mesa of silicon dioxide-nitride structure (Fig. 6B).
  • the structure is oxidized at a high temperature, in the range of 1000- 1100oC, growing the final field oxide regions such that the upper surfaces of these grown regions are coplanar with the active surface of the silicon 10.
  • the high temperature oxidation has the advantage of forming a 10,000-13,000 Angstrom oxide 24 (Fig. 9) in about 7-10 hours as compared to the time of 15-24 hours formation time required for low temperature oxide 21 (Fig. 7).
  • Fig. 9 Since the just-mentioned oxidation is accomplished at a high temperature, and the silicon substrate where the field oxide is to be formed is no longer doped, the bird's beak and bird's head characteristics of prior art methods will be inherently formed near the pad oxide sidewalls. However, the final structure that results from this process shown in Fig. 9 will have the advantage of being substantially coplanar.
  • the present invention may also be conveniently extended to achieve another extremely important aspect of integrated circuits. This aspect is the provision of doping the silicon substrate beneath the field isolation oxide regions 18 (Fig. 8) or 21 (Fig. 7), often referred to as a parasitic channel stopper doping.
  • Parasitic channel stopper doping is important for eliminating unwanted conduction due to inversion under the field isolation when undoped or lightly doped substrates are employed.
  • the use of lightly doped substrates is practiced in order to reduce diffused line capacitance which degrades performance as well as reducing hot electron effects which degrade reliability.
  • n-type parasitic channel stopper doping is to be provided, which is typically the case when p- channel field effect transistor devices are intended to be formed on the resulting structure
  • the present process is modified such that, for example, when arsenic is used to dope the field isolation oxide regions, the arsenic ion implantation energy, dose, drive-in temperature and time and the parameters associated with the final field oxidation step are so adjusted that after the completion of the field oxidation an adequate amount of arsenic is left behind to form an effective channel stop under the field oxide.
  • boron penetration depth is adjusted to be greater than the arsenic penetration depth such that after the final field oxidation step, fully leaking out the arsenic, boron is left beneath the thick oxide.
  • the active devices of the integrated circuit may be completed using conventional integrated circuit fabrication techniques. These techniques, of course, include diffusion and/or ion implantation of regions of the coplanar structure.
  • Fig. 10 One such completed device of the MNOS type formed on a true coplanar structure of the present invention is shown in Fig. 10.
  • the silicon substrate 10 is of p-type.
  • a source 25 and a drain 26 having n-type impurities are formed in the substrate 10 defining a channel region 27 therebetween.
  • a first insulating layer 28 made of, for example, silicon dioxide, a second insulating layer 29 made of, for example, silicon nitride, and a control gate 30 made of, for example, polycrystalline silicon, are formed in order such that the resulting gate structure is in a self-aligned relationship with the source 25 and drain 26.
  • Reference numeral 31 indicates an insulating layer made of, for example, phosphosilicate glass for electrically isolating the metal (typically, aluminum) connections 32, 33 and 34 electrically connected to the source 25, drain 26 and "the control gate 30, respectively.
  • metal typically, aluminum
  • Reference numeral 31 indicates an insulating layer made of, for example, phosphosilicate glass for electrically isolating the metal (typically, aluminum) connections 32, 33 and 34 electrically connected to the source 25, drain 26 and "the control gate 30, respectively.

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Abstract

Dans un procédé de fabrication d'une structure de circuits intégrés, une couche d'oxyde (11) est déposée sur un substrat de silicium, une couche de nitrure de silicium (12) est déposée sur la couche d'oxyde et on établit ensuite des motifs de masque de photo-réserve (14) utilisés pour attaquer la couche de nitrure (12) de manière que le masque (14) présente un bord saillant au-delà de la couche de nitrure (12). Le substrat est ensuite soumis à une implantation ionique, les régions sous-jacentes au masque (14) étant protégées de l'implantation. Les ions implantés sont ensuite diffusés sur une distance prédéterminée au-dessous du masque (14). On effectue ensuite une oxydation à une température comprise entre 700 et 800oC, les vitesses différentielles d'oxydation du silicium dopé et non dopé permettant de réduire la formation de caractéristiques indésirables de "tête d'oiseau" et "bec d'oiseau" dans l'oxyde résultant (18). Pour former une véritable structure coplanaire, l'oxyde formé (18) est enlevé, on effectue une implantation ionique ultérieure en utilisant le nitrure (12) en tant quemasque et l'on effectue une étape d'oxydation ultérieure. D'une manière alternative, on peut utiliser pendant la deuxième étape d'oxydation une région dopée non oxydée résultant de l'implantation ionique initiale.In a method of manufacturing an integrated circuit structure, an oxide layer (11) is deposited on a silicon substrate, a layer of silicon nitride (12) is deposited on the oxide layer and then established photoresist mask patterns (14) used to attack the nitride layer (12) so that the mask (14) has a protruding edge beyond the nitride layer (12). The substrate is then subjected to an ion implantation, the regions underlying the mask (14) being protected from implantation. The implanted ions are then diffused over a predetermined distance below the mask (14). Oxidation is then carried out at a temperature between 700 and 800oC, the differential oxidation speeds of doped and undoped silicon making it possible to reduce the formation of undesirable characteristics of "bird's head" and "bird's beak" in the resulting oxide (18). To form a true coplanar structure, the oxide formed (18) is removed, a subsequent ion implantation is carried out using the nitride (12) as a mask and a subsequent oxidation step is carried out. Alternatively, a non-oxidized doped region resulting from the initial ion implantation can be used during the second oxidation step.

Description

PROCESS FOR MANUFACTURING AN INTEGRATED CIRCUIT STRUCTURE
Technical Field
This invention relates to processes of the kind for forming an oxide region in a portion of a semiconductor substrate, including the steps of: forming a silicon oxide layer on a surface of said substrate and forming a silicon nitride layer on a portion of said oxide layer and having edges defining an active area of the substrate.
Background Art
A process referred to as the LOCOS process is known from the publication "Local Oxidation of Silicon: New Technological Aspects" by J. A. Appels et al, Philips Research Reports 26, pages 157-165, June 1971. According to the known process, relatively thick oxide patterns are partly or fully countersunk in the silicon substrate by utilizing the composite silicon oxidesilicon nitride layer as an oxidation mask. If the composite silicon oxide-silicon nitride layer is first used as an etchant mask before oxidation then a fully countersunk oxide pattern is obtained. However, as explained in the aforementioned publication in the known process, during oxidation an undesired oxide extension known as the "bird's beak" grows underneath the silicon nitride mask. Furthermore where some silicon is etched away before oxidation a bump, which may be of the order of 4,000-5,000 Angstroms in height is formed in the edge of the thick oxide layer adjoining the oxidenitride mask.
Typically, the bird's beak is formed in the recessed oxide during oxidation and results from lateral diffusion underneath the silicon dioxide (also known as pad oxide) which is formed between the silicon substrate and the silicon nitride. The bird's head results from the higher specific volume of the silicon dioxide than silicon and the lateral oxidation which occurs at the sidewalls of the recess. The silicon dioxide pad is used to prevent damage to the underlying silicon substrate by minimizing the stresses created on the substrate by the silicon nitride-silicon interface. Such stresses induce dislocations in the silicon substrate which result in undesirable leakage current channels and otherwise have a deleterious effect on the electrical characteristics of the interface.
The existence of the bird's beak or bird's head incurs many disadvantages. The device active area is reduced and the field isolation area is increased by the bird's beak. This is disadvantageous since chip real estate, particularly in very large scale integrated circuits, is at a premium. Because of the bird's beak, it is difficult to achieve well-defined lateral isolation boundaries. Because of the abrupt inclinations of the recessed oxide due to the bird's head, electrode interconnections formed on the recessed oxide regions are prone to be fractured and disconnected. Another disadvantage of having the bird's head is that the close contact with a mask pattern necessary for photolithographic processing is difficult to achieve. The foregoing are representative of the numerous disadvantages associated with the bird's beak and bird's head. It is, thus, readily apparent that it is desirable to reduce or eliminate the bird's beak and bird's head. A process of the kind specified is known from
U.S. Patent Specification No. 3,958,040. According to this known process, recesses are etched in the silicon substrate where fully recessed oxide is desired. Then an additional nitride mask is provided on the side walls of the recesses to protect the underlying silicon against oxidation, thereby reducing the bird's head formation. By providing the additional mask to adjoin the nitride layer of the first mask, it may be possible to reduce the extent of the bird's beak as well as the bird's head. The known process has the disadvantage that control of the bird's head problem is limited since when etching the recesses in the silicon some silicon will tend to remain on the underside of the mask overhang. If it is attempted to severely over-etch the substrate to fully remove such remaining silicon then the overhanging mask may collapse. Another disadvantage is that the nitride mask over the sidewalls of the recesses has only a limited degree of effectiveness during the oxidation step.
A further disadvantage is that only limited control of the bird's beak problem is achieved by the known process because some lateral oxidation of the silicon oxide layer of the composite mask still occurs.
Disclosure of the Invention
It is an object of the present invention to provide a process of the kind specified capable of providing a high degree of control over bird's head and bird's beak formation.
According to the present invention, there is provided a process of the kind specified, characterized by the steps of: forming a mask on said nitride layer having at least one edge projecting a predetermined distance beyond said nitride layer; forming a doped region in said substrate having an edge the location of which relative to an edge of said nitride layer is determined by the projecting edge of said mask; and thermally oxidizing said substrate thereby converting at least a portion of said doped layer to an oxide region.
It is found that a process according to the invention has the capability of significantly reducing both the bird's beak and the bird's head. A further advantage is the capability of precise control of active region dimensions. Preferably, the step of thermally oxidizing the substrate is effected at a temperature of below about 800ºC. A preferable range for such thermal oxidation is 700-800ºC.
Brief Description of the Drawings
Figs. 1-7 are cross-sectional representations of the sequential stages of fabricating a true coplanar semiconductor structure using the processes of the present invention. Figs. 1, 2, 3A, 5A, 6A and 7 are cross sectional representations of forming a true coplanar structure using an alternative process of the present invention.
Figs. 1-5 and 8 are cross-sectional representations of the sequential stages of fabricating a standard coplanar semiconductor structure using a process of the present invention.
Figs. 1-5, 6B, and 9 are cross-sectional representations of the sequential stages of forming a true coplanar semiconductor structure having a bird's beak and/or bird's head using a modified process.
Fig. 10 is a cross-sectional representation of a true coplanar structure fabricated in accordance with the present invention showing a conventional integrated circuit formed thereon.
Best Mode for Carrying Out the Invention
The invention will now be described, by way of examples, with reference to the accompanying drawings. Table I is an outline of the process sequence for forming a standard coplanar structure having a reduced bird's beak and bird's head in accordance with the present embodiment. In Table I, Steps 1 to 8 and 13 refer to the standard coplanar structure and steps 1 to 13 refer to the tτue coplanar structure. While the following description is primarily directed toward the fabrication of the standard and true coplanar integrated circuit structures, this description is exemplary of the fabrication of a class of integrated circuit structures which embody the principles of the present invention. In addition, it should be noted that although the thickness and other dimensions shown in the drawings herein are selected for clarity of illustration and not to be interpreted in a limiting sense there are a number of parameters whose dimensions are important.
Standard Coplanar Structure
The starting material is a slice of n-type or p-type monocrystalline semiconductor grade silicon. The starting material can be of either (111) or (100) orientation and has a bulk resistivity typically of 8-12 ohmcentimeter. In the Figures, the substrate 10 represents only a very small undivided part of the slice, perhaps 1 mil (about 25.4 microns) wide for each part. After appropriate cleaning, the slice is oxidized (step 2) by exposing, typically, to pure, dry oxygen at a rate of 5 liters per minute in a furnace tube at an elevated temperature of perhaps 850-1000ºC to produce an oxide layer 11 (Fig. 1) over the entire slice to a thickness of about 100-500 Angstroms. The thermal oxidation may be accomplished at atmospheric pressure or at a high pressure of up to 7 atmospheres. The oxide layer 11 (also referred to herein as pad oxide) may also be formed by wet oxidation by passing oxygen gas through water maintained at 97°C, at the same flow rate as before, prior to admitting the oxygen into the furnace tube. The temperature of wet oxidation is also in the range of 850-1000°C.
After oxidation, as illustrated in Fig. 1, a silicon nitride layer 12 is deposited (step 3) on the silicon slice, by low temperature chemical vapor deposition (LPCVD) using a mixture of ammonia and dichlorosilane at a temperature of about 700ºC and a pressure of 400 millitorr. A typical ratio of ammonia to dichlorosilane is 3.5:1. The thickness of nitride 12 formed in this manner is typically in the range of 700-1800 Angstroms. The lower limit here corresponds to the minimum thickness of the nitride needed to avoid defects in the nitride through which unwanted oxygen penetration may occur at a subsequent stage of fabrication of the present device. Beyond 1800 Angstroms the nitride 12 may strain the surface of the silicon substrate 10 to a degree that the substrate surface will develop dislocations and defects resulting in unwanted junction leakage. Next, in order to increase the adhesion of the next to be deposited photoresist layer to the nitride layer 12, the surface portion of the nitride layer may be oxidized (step 4) to form a thin surface layer 13 (Fig. 1) of silicon dioxide. This may be done by treating the nitride 12 with steam at 750-1000ºC or by LPCVD at a temperature of 400-500ºC for a time sufficient to form a silicon dioxide layer 13 of about 50-100 Angstroms thickness. Although this step is not essential to the concept of the present invention per se, it is believed preferable to use this step to enhance adhesion of the nitride 12. to the next to be formed photoresist layer.
Next, as shown in Fig. 2, a layer of photoresist 14 of typical thickness in the range 6,000-10,000 Angstroms is applied over the entire surface of the resulting structure using a conventional process, then exposed to ultraviolet light through a mask which defines the desired pattern of the device active area. The photoresist is then developed by using a suitable solvent exposing the areas where the nitride is to be etched away. Before etching the nitride, if the thin layer 13 of oxide was formed on the nitride 12, then this thin oxide layer is removed by dipping the slice in a dilute hydrofluoric acid solution. The nitride layer 12 is then etched (step 5) using the overlying photoresist 14 (Fig. 2) as a mask by a conventional etching technique such as plasma etch or a wet chemical etch.
The nitride etch discussed in the previous step is accomplished in a controlled manner such that the nitride 12 is undercut resulting in a critical overhang 14A of length XL p of the photoresist 14 past the edge of the nitride 12 as shown in Fig. 2. The length of the overhang XL P is the distance between edge 16 of the photoresist overhang 14A and edge 17 of the nitride mask 12. This photoresist overhang 14A is necessary to protect the regions of the substrate directly beneath the nitride-oxide dual mask from being doped in the next to follow ion implantation step of the present process as fully explained hereiribelow. The length XLP of the overhang chosen for reducing the bird's beak and bird's head is a function of such parameters as the ion implantation energy, dose and drive-in depth which will become meaningful subsequently.
After patterning the active region in the manner described above, as shown in Fig. 3, the structure is subjected to a conventional ion implantation step (step 6) whereby, for example, arsenic ions of a high energy in the range 80-100 Kev and dose 8 x 10 15 ions per square centimeter are introduced into the unmasked regions of the substrate through the oxide layer 11. Other suitable dopants include phosphorus. The profile of the dopant following this implantation step is shown in Fig. 3 by numeral 15. During this doping step, the areas of the substrate where the bird's beak and bird's head are generally formed, namely, the areas of the substrate directly beneath the photoresist overhang 14A and between the boundary lines 16 and 17, are protected by the photoresist overhang 14A and thus are not doped.
Next, the photoresist 14 is removed and the implanted arsenic ions are diffused (step 7) into the substrate to a predetermined junction depth XJ as shown in Fig. 4, which is an enlarged illustration of a section of the structure shown in Fig. 3, using a conventional diffusion process. The profile of the dopant following the diffusion step is shown in Fig. 4 by numeral 15A. The junction depth X. is determined by the thickness tox of the recessed isolation oxide. The thicker the isolation oxide needed, the greater the depth Xj. Typically, the thickness of the doped silicon consumed during oxidation (step 8) is about 50% of the silicon dioxide grown therefrom, or
Xj = 0.5tox (1) For example, for growing a 10,000 Angstrom thick isolation oxide, the ions are diffused preferably to a depth Xj of about 0.5 microns. To diffuse arsenic ions to a depth Xj of 0.5 microns, the implanted structure is subjected to a temperature of 1000ºC in a nitrogen atmosphere for about 120 minutes. During this diffusion step/ the arsenic ions diffuse not only in the vertically downward direction but also laterally. The sideways diffusion distance Xd, which is measured from the boun dary line corresponding to the edge I7 orf the overhang 14A (Fig. 4) is a function of the dopant dose and is generally less than the vertical diffusion distance Xj. For a dose D1 of 8 x 1015 ions/cm2, Xd is about 70% of the vertical diffusion. Or Xd = 0.7Xj (2)
In other words, if the arsenic is to be diffused downward into the substrate to a depth Xj of 0.5 microns, the corresponding sideways diffusion distance Xd would be about 0.35 microns. When a smaller dose of arsenic ions is used, the sideways diffusion distance Xd would, of course, be less. For example, for a dose D2 of about 10 15 ions per square centimeter, the sideways diffusion would be only about 50% of the vertical diffusion. Or
Xd = 0.5Xj (3.) Combining equations (1) and (2), a direct relationship between Xd and tox for an ion dose D1 is obtained as
Xd = 0.35tox (4)
The corresponding relation for the lower ion dose D2, which is obtained by combining equations (1) and (3) is
Xd = 0. 25tox (5 )
Thus, for the exemplary ion dose of 8 x 1015 ions/cm2 and oxide thicknesses of 10 , 000 Angstroms (1 micron) and 13 , 000 Angstroms ( 1.3 microns ) , the latbearal a31.ffaa.sion distance would be 0.35 microns and -0.45 micr ons, respectively. For the lower dose of 1 ac 10 ions/cm2, the lateral diffusion distance corresponding to the isolation oxide thickness of 10,000 Angstroms (1 micron) and 13,000 Angstroms (1.3 microns) are, respectively, 0.25 microns and 0.32 microns.
The length XL p of the overhang 14A is arranged preferably to be somewhat less than the lateral diffusion distance X,. When XL P is less than Xd, the area of the substrate directly beneath the nitride is not doped during the implantation step (step 6), although the areas of the substrate beneath the nitride 12 and interior to the nitride boundary 17-17 may be doped during the diffusion step (step 7). However, the doping in the regions just mentioned is light compared to that in the regions outside the boundary 17-17, providing rapid oxidation outside the boundary 17-17 and slower oxidation beneath the nitride 12 during the next-to-follow oxidation step (step 8) thereby substantially eliminating the bird's beak and bird's head. When XL P is equal to or greater than Xd, the substrate area directly beneath the nitride 12 is not doped during either the implantation step (step 6) or the diffusion step (step. 7). This provides rapid oxidation outside the nitride boundary 17-17 and slower oxidation beneath the nitride 12 and thereby eliminates the bird's beak and bird's head. However, in all these three situations there may result, due to an excessive over-etching of the nitride 12, a nitride-edge which will be ragged and/or illdefined. Such an improperly cut nitride mask will imprecisely define the active region causing design rule errors in subsequent device fabrication. At any rate, it has been found that excellent bird's beak and bird's head suppression is obtained for the exemplary para- meters such as D = 8 x 10 15 ion/cm2, tox = 10,000 Angstroms, X. = 0.5 microns, X, = 0.35 microns when XT**5 was in the range of (0.1-0.2) microns. Following, the diffusion of the arsenic ions to the desired junction depth, a low temperature steam oxidation is accomplished (step 8) to grow the thick field oxide regions 18 (Fig. 5) in the doped areas 15-15 (Fig. 4) of the substrate by consuming the silicon therein. The temperature selected for this oxidation step is in the range 700-800°C and the time of oxidation is about 15-24 hours depending on the thickness of the field oxide regions 18 desired. During this low temperature oxidation step, oxidation of the undoped regions of the substrate will be minimal thereby suppressing the bird's beak and bird's head. The suppression of bird's beak and bird's head is achieved because silicon dioxide has different growth rates depending upon the silicon surface on which it is formed. The growth rate of silicon dioxide from the highly doped silicon region 15- 15 is significantly greater than that of the intrinsic or undoped silicon corresponding to the nitride mask 12. The growth rate is a function of the crystal orientation of the doped silicon surface, the rate for (111) surface being about 10-20% higher than that for a (100) surface and also the energy and dose of the ions used for doping (if accomplished by ion implantation) the silicon. For example, when arsenic ions of 100 keV energy and 8 x 10 15 ions per square centimeter dose are used to dope a (100) silicon, the oxide growth rate in the doped regions at the low temperature of 750ºC is about 5-6 times higher than in the undoped regions of the same material. In general, the oxide growth rate increases as the impurity concentration increases. The difference in oxidation rate between doped and undoped silicon also increases as the oxidation temperature becomes lower. Hence a lower temperature is more advantageous for the performance of this invention. However, when the temperature for thermal oxidation is excessively low, the period of time required for the oxidation is too long which creates a problem from the industrial point of view of requiring a round-the-clock attention. In practice, the temperature for the thermal oxidation in accordance with this invention, as already mentioned, lies between 700°C and 800°C when the ambient pressure is about one atmosphere since under these conditions it is possible to grow a 10,000-12,000 Angstrom thick field isolation oxide within a more manageable time of about 15-24 hours. It is appreciated that the oxidation rate becomes greater with increasing ambient pressure and the oxidation time can be made shorter or the oxidation temperature may be lowered below 700°C for a predetermined thickness. Thus, in this invention, the substrate areas where bird's beak and bird's head are formed are protected from doping during the ion implantation step and the diffusion step by means of the photoresist overhang 14A and then, by conveniently employing the different growth rates of silicon dioxide in doped/undoped silicon, the growth of bird's beak and bird's head is considerably decreased.
The thickness of the field oxide regions 18 (Fig. 5) grown as explained above is typically in the range of 10,000-12,000 Angstroms. After growing the field oxide regions 18, the oxide-nitride dual mask 11-12 is removed in the usual manner by first dipping the structure in dilute hydrofluoric acid to remove any oxide film that is formed over the nitride 12 during the previous oxidation step, then subjecting the nitride to an etchant such as hot phosphoric acid or a plasma which removes the nitride but not the silicon dioxide, followed by a re-dipping in dilute hydrofluoric acid to remove the pad oxide 11. Thereafter, the exposed silicon is cleaned. The resulting structure is an improved standard coplanar structure, shown in Fig. 8, having a suppressed bird's beak and bird's head.
Example 1 Standard Coplanar Structure In a specific example of the process for forming a standard coplanar structure having about 10,000 Angstroms thick isolation oxide regions with a suppressed bird's beak and bird's head as exemplified by the process discussed above, after forming a 500 Angstrom thick pad oxide (11) and an i800 Angstrom thick nitride (12) composite mask (steps 2 and 3) on an n-type silicon substrate, the active region was patterned (step 5) using a photoresist 14 of thickness of about 8,000 Angstroms. Then, the nitride 12 was etched from the field regions, simultaneously creating the photoresist overhang 14A of length XL P in the range of about (0.1-
0.2) microns. Next, arsenic ions of energy 100 keV and dose about 8 x 10 15 ions per square centimeter were implanted in the field regions (step 6). Thereafter, the arsenic ions were diffused into the silicon sub strate to a depth of about 0.5 microns by subjecting the structure to a temperature of about 1000ºC for about two hours in a nitrogen environment ( step 7 ). For the ion dose and energy, diffusion time and temperature chosen in this example, the sideways diffusion Xd of arsenic was about 0.35 microns. Then, the doped field regions were oxidized at a temperature of about 750ºC for a period of about 20 hours, fully converting the doped silicon surface into a 10,000 Angstrom thick field oxide (step 8). The pad oxide 11 and nitride 12 were then removed (step 13).
True Coplanar Structure in order to form a true coplanar structure having recessed oxide regions fully set below the substrate surface, in an alternative method of practicing this invention, the above process described in connection with the standard coplanar structure and summarizedin Table I may be continued in the following manner after the low temperature oxidation step (step 8, in Table I) in which doped regions of the substrate are fully converted into field isolation oxide regions 18 (Fig. 5). The complete sequence of steps (steps 1-13) of forming the true coplanar structure in accordance with this method is provided in flowchart form in Table I.
After step 8, the thick field oxide formation (Fig. 5) surface is subjected to dilute hydrofluoric acid etch (step 9) for about 6-7 minutes to remove the field oxide and thereby form a mesa of silicon (10)- silicon dioxide (11)-silicon nitride (12) as shown in Fig. 6. The oxide etch in this step not only removes substantially all the field oxide 18 forming the recesses 20 in the substrate, but also forms the nitride overhang 12A. - As shown in Fig. 6, the nitride overhang 12A is tailored, by controlling the etch time in step 9, to have an overhang length XL n. The length XL n of the overhang 12A is chosen such that the substrate regions beneath regions 11A of the pad oxide 11 where the bird's beak and bird's head are generally formed are protected from doping during the second field doping (steps 10 and 11) discussed below. This is analogous to the protec- tion of substrate region beneath the nitride 12 and interior to the nitride boundary 17-17 (Fig. 3) during the previously described fabrication process of Table I, step 5. The length XL n, like the photoresist overhang length XL P discussed in connection with step 5 above and for the reasons discussed therein, is arranged to be somewhat less than the lateral diffusion distance Xd, of the dopant at the completion of the diffusion step 11 discussed, below. As discussed in connection with the photoresist overhang length XL P, the value of the nitride overhang length XL n which is necessary to suppress the bird's beak and bird's head is also ultimately determined by the thickness of the final field isolation oxide. At any rate, it has been found that excellent bird's beak and bird's head suppression is obtained for the exemplary parameters such as the vertical drive in depth Xj (at the completion of step 10) of about 0.5 microns (which dimension is chosen to grow a 10,000 Angstrom thick final isolation oxide) and the lateral diffusion Xd (at the completion of step 11) of about 0.35 microns when X L n is about (0.1-0.2) microns.
Next, a dopant such as arsenic or phosphorus is ion implanted in the field regions (step 10). Arsen ic ions of a relatively low energy in the range of 30-50 KeV and a dose preferably of the same value as in the first implantation (step 6, Table I) of 8 x 1015 ions per square centimeter are used in this implantation step. Lower energy arsenic ions are selected for the present field doping step than those used in step 6, since now the photoresist layer 14 (Figs. 2-4) is no longer present to protect the active region from high energy ion implantation. The energy selected in the present step, which is governed by the thickness of the nitride mask 12, is such that arsenic ions will not penetrate the nitride mask 12.
After the low energy ion implantation in the field regions, the structure is subjected to a high temperature diffusion (step 11) using the same conditions as explained in connection with step 7 above to diffuse the ions into the recesses 20 of the substrate.
Next, a low temperature oxidation (step 12), which can use the same conditions as those discussed above in connection with the first field oxidation (step 8) is achieved to grow the final field oxide regions 21 shown in Fig. 7. As explained previously, the combination of protecting the substrate regions beneath the pad oxide regions 11A from doping and oxidizing the structure at a low temperature substantially suppresses the bird's beak and bird's head formation. The low temperature oxidation of the present process step is continued for about 15-24 hours until the upper surface of the field isolation oxide regions matches the surface of the active region of the silicon substrate 10. Thereafter, the oxide-nitride composite mask 11-12 is removed (step 13) in a conventional manner as fully explained above in connection with the standard coplanar structure. The resulting structure as illustrated in Fig. 7 has a true coplanar surface with a plurality of recessed oxide isolation regions 21.
Example 2 True Coplanar Structure
In a specific example of forming a true coplanar structure having a suppressed bird's beak and bird's head as exemplified by the process discussed immediately above, first steps 1 through 8 as described in Example 1 were accomplished. Then, the newly-grown oxide 18 (Fig. 5) was etched (step 9) using a conventional oxide etchant forming a mesa of silicon (10)- silicon dioxide (11)-silicon nitride (12) (Fig. 6) wherein the nitride 12 was tailored to overhang the pad oxide 11 to a distance of about 0.1 micron. The field regions, 20 (Fig. 6) were then ion implanted (step 10) by means of arsenic ions of energy of about 40 keV and dose about 8 x 10 ions per square centimeter. Thereafter, the arsenic ions were diffused into the substrate (step 11) using the same conditions explained above in connection with this Example 2 to a depth of about 0.5 microns. This particular junction facilitated growing a 10,000 Angstrom thick final isolation oxide 21 (Fig. 7). Following the diffusion of arsenic, a second low temper- ature oxidation (step 12) using the same conditions as explained above in connection with the present Example was accomplished growing the field oxide regions 21 (Fig. 7) until the upper surface of these oxide regions matched the active region of the silicon substrate. The oxide (11)-nitride (12) -mask was then removed.
True Coplanar Structure (Alternative Process) An alternative method of forming a true coplanar structure having a suppressed bird's beak and bird's head in accordance with the present invention is illustrated in a flowchart sequence in Table II, below. The steps of this alternative method are: after the high energy ion implantation (step 6) in the field regions, diffusing the ions into the substrate to a substantially greater depth than before (step 7'); partially converting (i.e. converting the upper portion of) the doped substrate to oxide (step 8') thereby leaving a residual amount of dopant in the substrate; and etching the oxide grown in step 8' (step 9'). The second implantation and diffusion steps (steps 10 and 11 Table I) are eliminated. Instead, the substrate areas where a residual dopant remained after the oxidation (step 8'), are reoxidized fully converting the doped silicon to oxide (step 10). Finally, the oxide-nitride mask is removed.
As illustrated in Table II, the sequence of steps in this method follows the sequence of the previous method of forming a true coplanar structure described above and illustrated in Table I through the step of ion implantation in the field regions (step 6, Table I). The energy and dose of ions used in this implantation step are the same as before, namely, when arsenic dopant is utilized, of about 80-100 keV and 8 x 10 ions per square centimeter, respectively. The arsenic diffusion (step 7') departs from the previous process in that after implantation, the arsenic ions are driven deep into the silicon material (Fig. 3A) in the areas where the field oxide is to be formed, e.g., using a temperature of 1000ºC in a nitrogen atmosphere for a period of 2.5-4 hours such that the junction depth is in the range of (0.7-1) microns. The lower limit corresponds to forming a recessed isolation oxide of thickness of about 10,000 Angstroms. The upper limit corresponds to an oxide thickness of about 13,000 Angstroms. Thereafter, referring to Fig. 5A, a low temperature steam oxidation (step 8'), at a temperature in the range 700-800ºC for about twenty-four hours is applied to partially convert the doped silicon to silicon dioxide, leave some arsenic dopant in the lower strata of substrate 10 where the dopant was introduced during the implantation and diffusion steps (steps 6 and 7', respectively). Specifically, during this oxidation step (step 8'), about half of the doped silicon is converted to silicon dioxide leaving behind in the substrate a doped layer of a thickness in the range of about (0.35- 0.5) microns. The exact thickness of the doped silicon left after the oxidation step 8' is determined by the final isolation oxide thickness desired and the amount of silicon dioxide that is to be left behind after the next-to-follow etching step (step 9'). If during step 9, all of the grown oxide 18 (Fig. 5A) is to be removed, and if the desired final isolation oxide thickness is about 10,000 Angstroms, then a doped silicon of thickness of about 0.5 microns be left beneath the oxide regions 18 (Fig. 5A) after the oxidation step (step 8'). If, on the other hand, after the etching step (step 9') about a 2,000 Angstrom thick layer of oxide 18 is to be left behind, and if the desired final isolation oxide is again about 10,000 Angstroms, then a doped silicon of thickness of about 0.4 microns is sufficient. The thickness of the oxide 18 (Fig. 5A) grown is typically in the range of 10,000-13,000 Angstroms. Next, the grown oxide 18 is etched (step 9') in a conventional manner resulting in the recesses 20 in the substrate and a silicon (10)-oxide (11)-nitride (12) mesa (Fig. 6A). During this etching step, the sidewalls 19 (Fig. 5A) of pad oxide 11 are also etched away, thus eliminating the presence of any possible arsenic that may have entered the sidewalls during the implantation. This etching step insures against possible oxide growth from the silicon near the sidewalls 19 (Fig. 5A) in the next-to-follow oxidation step. A significant difference of this alternative process of forming a true coplanar structure from the true coplanar process summarized in steps 1-13 of Table I is that in this process the second implantation and diffusion steps (steps 10 and 11, Table I, respectively) are eliminated. These steps are eliminated because at the completion of the etching step (step 9', Table II), the etched upper surfaces 23 (Fig. 6A) of the silicon in the locations where arsenic was introduced in the implantation-diffusion steps (steps 6 and 7) retain intact a residual arsenic discussed above. These surfaces 23 (Fig. 6A) of silicon are then oxidized at a low temperature of 750°C for a period of 15-24 hours fully consuming the doped silicon and until the surface of the field oxide regions is coplanar with the active surface of the substrate 10.
Example 3 True Coplanar Structure In a specific example of the alternative process for forming a true coplanar structure having a suppressed bird's beak and bird's head as exemplified by the process discussed immediately above relative to Table II, the steps of Example 2 above through the step of arsenic diffusion (step 6) were carried out. After arsenic ion implantation (and removal of the photoresist 14), the arsenic ions were diffused at 1000ºC for about 2.5 hours such that the junction depth, (Fig. 3A) at the completion of this step was about 0.8 microns (step 7', Table II). Next, using a 750ºC temperature wet oxidation for about twenty-four hours, the thick oxide regions 18 (Fig. 5A) of thickness of about 9,000 Angstroms were grown converting about 0.4 microns thickness of the doped upper layer silicon in regions 22 (Fig. 3A) to silicon dioxide (step 8'). Thereafter, oxide 18 was etched (step 9') forming a silicon-oxide-nitride mesa (Fig. 6A) . Next, a second low temperature oxidation, using the same conditions as before, was accomplished growing the final isolation oxide regions 21 of thickness of about 10,000 Angstroms (Fig. 7) while fully consuming the remaining 0.4 microns thick doped silicon material in regions 23 (Fig. 6A) (step 10'). Thereafter the oxide-nitride mask was removed (step 11').
The above described process may be modified to construct a planar structure where suppression of bird's beak and bird's head is not a concern. This is achieved by following the process sequence shown in Table I through step 9, the step of etching the grown oxide and forming the mesa of silicon dioxide-nitride structure (Fig. 6B). After this etching step, the structure is oxidized at a high temperature, in the range of 1000- 1100ºC, growing the final field oxide regions such that the upper surfaces of these grown regions are coplanar with the active surface of the silicon 10. The high temperature oxidation has the advantage of forming a 10,000-13,000 Angstrom oxide 24 (Fig. 9) in about 7-10 hours as compared to the time of 15-24 hours formation time required for low temperature oxide 21 (Fig. 7).
Since the just-mentioned oxidation is accomplished at a high temperature, and the silicon substrate where the field oxide is to be formed is no longer doped, the bird's beak and bird's head characteristics of prior art methods will be inherently formed near the pad oxide sidewalls. However, the final structure that results from this process shown in Fig. 9 will have the advantage of being substantially coplanar. The present invention may also be conveniently extended to achieve another extremely important aspect of integrated circuits. This aspect is the provision of doping the silicon substrate beneath the field isolation oxide regions 18 (Fig. 8) or 21 (Fig. 7), often referred to as a parasitic channel stopper doping. Parasitic channel stopper doping is important for eliminating unwanted conduction due to inversion under the field isolation when undoped or lightly doped substrates are employed. The use of lightly doped substrates is practiced in order to reduce diffused line capacitance which degrades performance as well as reducing hot electron effects which degrade reliability.
When n-type parasitic channel stopper doping is to be provided, which is typically the case when p- channel field effect transistor devices are intended to be formed on the resulting structure, the present process is modified such that, for example, when arsenic is used to dope the field isolation oxide regions, the arsenic ion implantation energy, dose, drive-in temperature and time and the parameters associated with the final field oxidation step are so adjusted that after the completion of the field oxidation an adequate amount of arsenic is left behind to form an effective channel stop under the field oxide.
When p-type parasitic channel stopper doping is to be provided, which is typically the case when n- channel field effect transistor devices are desired on the resulting structure, however, an initial boron implantation and drive-in will have to be accomplished before the arsenic implantation of step 6. The boron penetration depth is adjusted to be greater than the arsenic penetration depth such that after the final field oxidation step, fully leaking out the arsenic, boron is left beneath the thick oxide.
Utilizing the structures of Figs. 7 or 8, the active devices of the integrated circuit may be completed using conventional integrated circuit fabrication techniques. These techniques, of course, include diffusion and/or ion implantation of regions of the coplanar structure.
One such completed device of the MNOS type formed on a true coplanar structure of the present invention is shown in Fig. 10. In this Figure, the silicon substrate 10 is of p-type. A source 25 and a drain 26 having n-type impurities are formed in the substrate 10 defining a channel region 27 therebetween. On the channel region 27, a first insulating layer 28 made of, for example, silicon dioxide, a second insulating layer 29 made of, for example, silicon nitride, and a control gate 30 made of, for example, polycrystalline silicon, are formed in order such that the resulting gate structure is in a self-aligned relationship with the source 25 and drain 26. Reference numeral 31 indicates an insulating layer made of, for example, phosphosilicate glass for electrically isolating the metal (typically, aluminum) connections 32, 33 and 34 electrically connected to the source 25, drain 26 and "the control gate 30, respectively. After a number of such devices are formed, they may be interconnected by conventional integrated circuit metallization subsequently formed on the surface of the semiconductor structure. The interconnections, because of the reduced bird' s head and the true coplanar nature of the structure resulting from this invention will not be subjected to the previously-mentioned problems. Also, because of the remarkable reduction in bird's beak and the consequent more precise isolation of adjacent devices, the device packing density is increased.

Claims

CLAIMS :
1. A process for forming an oxide region in a portion of a semiconductor substrate (10), including the steps of: forming a silicon oxide layer (11) on a surface of said substrate (10) and forming a silicon nitride layer (12) on a portion of said oxide layer (11) and having edges defining an active area of the substrate, characterized by the steps of: forming a mask (14) on said nitride layer (12) having at least one edge projecting a predetermined distance beyond said nitride layer (12); forming a doped region in said substrate (10) having an edge the location of which relative to an edge of said nitride layer (12) is determined by the projecting edge of said mask (14); and thermally oxidizing said substrate (10) thereby converting at least a portion of said doped layer to an oxide region (18).
2. A process according to claim 1, characterized in that said step of thermally oxidizing said substrate (10) is effected at a temperature of below about 800ºC.
3. A process according to claim 1, characterized in that said step of forming a mask (14) includes the steps of forming a photoresist layer (14) having edges on said nitride layer (12) and etching said nitride layer such that at least one edge of said photoresist layer (14) projects beyond said nitride layer (12) by said predetermined distance.
4. A process according to claim 1, characterized in that said step of forming a doped region includes the steps of implanting ions in said substrate (10) such that the projecting edge of said mask (14) protects from doping the substrate (10) directly underneath the mask projecting edge; removing said mask (14);
4. ( concluded) and diffusing the implanted ions into said substrate (10) to a predetermined lateral distance beneath the location of the removed projecting edge of said mask (14).
5. A process according to claim 3, characterized in that said step of implanting ions includes implanting arsenic or phosphorus ions at an energy in the range of about 80-100 keV.
6. A process according to any one of claims 1 to 5, characterized in that said step of thermally oxidizing said substrate (10) is effective to oxidize only an upper part of said doped region and further characterized by the steps of removing the thus formed oxide region to expose a lower part of said doped region, and thermally oxidizing said substrate (10) at a temperature of below about 800ºC to convert said lower part of said doped region to form a further oxide region (21) having a surface substantially coplanar with a surface of said substrate.
7. A process according to any one claims 1 to 5, characterized by the steps of etching said oxide region (18) such that at least one edge of said nitride layer (12) projects beyond said oxide layer (11) by a predetermined amount; forming a further doped region in said substrate (10) having an edge the location of which relative to an edge of said oxide layer (11) is determined by the projecting edge of said nitride layer (12); and thermally oxidizing said substrate (10) at a tem- perature of below about 800ºC to form a further oxide region (21) having a surface substantially coplanar with a surface of said substrate (10).
8. A process according to claim 7, characterized in that said step of forming a further doped
8. (concluded) region includes the steps of implanting ions at an energy in the range of about 30-50 keV, and diffusing the thus implanted ions into said substrate (10) to a predetermined lateral distance beneath the edge of said nitride layer (12).
9. A process according to claim 6 or 7, characterized in that said steps of thermally oxidizing said substrate (10) are effected at temperatures in the range of about 700-800°C.
EP82902885A 1981-09-08 1982-09-02 Process for manufacturing an integrated circuit structure Expired EP0087462B1 (en)

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US06/300,318 US4372033A (en) 1981-09-08 1981-09-08 Method of making coplanar MOS IC structures
US300318 1981-09-08

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EP0087462B1 (en) 1989-04-12
EP0087462A4 (en) 1986-03-18
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DE3279613D1 (en) 1989-05-18
JPH0519308B2 (en) 1993-03-16
US4372033A (en) 1983-02-08

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